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Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring

We have designed and synthesized a new tris-chelating polypyridine ligand (bpy(3)Ph) suitable to be used as a bridging ligand (BL) for constructing various supramolecular photocatalysts. This BL is a phenylene ring with three ethylene chains at 1, 3, and 5 positions, of which the other terminals are...

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Autores principales: Cancelliere, Ambra M., Puntoriero, Fausto, Serroni, Scolastica, Campagna, Sebastiano, Tamaki, Yusuke, Saito, Daiki, Ishitani, Osamu
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7069366/
https://www.ncbi.nlm.nih.gov/pubmed/32206277
http://dx.doi.org/10.1039/c9sc04532e
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author Cancelliere, Ambra M.
Puntoriero, Fausto
Serroni, Scolastica
Campagna, Sebastiano
Tamaki, Yusuke
Saito, Daiki
Ishitani, Osamu
author_facet Cancelliere, Ambra M.
Puntoriero, Fausto
Serroni, Scolastica
Campagna, Sebastiano
Tamaki, Yusuke
Saito, Daiki
Ishitani, Osamu
author_sort Cancelliere, Ambra M.
collection PubMed
description We have designed and synthesized a new tris-chelating polypyridine ligand (bpy(3)Ph) suitable to be used as a bridging ligand (BL) for constructing various supramolecular photocatalysts. This BL is a phenylene ring with three ethylene chains at 1, 3, and 5 positions, of which the other terminals are connected to 2,2′-bipyridine moieties. The ligand bpy(3)Ph has been used to prepare, according to a multi-step synthetic protocol, trinuclear supramolecular photocatalysts containing different metal subunits. In particular, the compounds Ru2Re and RuRe2 have been prepared, containing different ratios of components based on Ru(dmb)(3)(2+)-type and Re(dmb)(CO)(3)Cl-type units (dmb = 4,4′-dimethyl-2,2′-bipyridine), which can play the roles of photosensitizers and catalyst units for photocatalytic CO(2) reduction, respectively. The trinuclear model Ru3 and mononuclear and dinuclear Ru and Ru2 precursor metal complexes, containing free chelating sites, have also been synthesized using the same bridging ligand. The absorption spectra, redox behaviour and photophysical properties of the new species indicate that there is no strong electronic interaction among the Ru and Re units. The trinuclear complexes Ru2Re and RuRe2 could photocatalyze CO(2) reduction to CO with high selectivity (up to 97%), high efficiency (Φ(CO)s of 28% and 25%, respectively: BIH as a reductant), and high durability (TON(CO)s of 5232 and 6038, respectively: BIH as a reductant) which are the largest TONs for CO(2) reduction using supramolecular photocatalysts in homogeneous solutions. The absence of negligible accumulation of the mono-reduced form of the photosensitizer indicates fast electron transfer to the catalyst unit(s) through the relatively large bridging ligand and is proposed to contribute to the outstanding photocatalytic properties of the new species, including their durability. The relevant photocatalytic behaviour of the new systems indicates new avenues for the design of extended bridging ligands capable of efficiently and functionally integrating photosensitizers and catalysts towards the preparation of new, larger supramolecular photocatalysts for selective CO(2) reduction.
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spelling pubmed-70693662020-03-23 Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring Cancelliere, Ambra M. Puntoriero, Fausto Serroni, Scolastica Campagna, Sebastiano Tamaki, Yusuke Saito, Daiki Ishitani, Osamu Chem Sci Chemistry We have designed and synthesized a new tris-chelating polypyridine ligand (bpy(3)Ph) suitable to be used as a bridging ligand (BL) for constructing various supramolecular photocatalysts. This BL is a phenylene ring with three ethylene chains at 1, 3, and 5 positions, of which the other terminals are connected to 2,2′-bipyridine moieties. The ligand bpy(3)Ph has been used to prepare, according to a multi-step synthetic protocol, trinuclear supramolecular photocatalysts containing different metal subunits. In particular, the compounds Ru2Re and RuRe2 have been prepared, containing different ratios of components based on Ru(dmb)(3)(2+)-type and Re(dmb)(CO)(3)Cl-type units (dmb = 4,4′-dimethyl-2,2′-bipyridine), which can play the roles of photosensitizers and catalyst units for photocatalytic CO(2) reduction, respectively. The trinuclear model Ru3 and mononuclear and dinuclear Ru and Ru2 precursor metal complexes, containing free chelating sites, have also been synthesized using the same bridging ligand. The absorption spectra, redox behaviour and photophysical properties of the new species indicate that there is no strong electronic interaction among the Ru and Re units. The trinuclear complexes Ru2Re and RuRe2 could photocatalyze CO(2) reduction to CO with high selectivity (up to 97%), high efficiency (Φ(CO)s of 28% and 25%, respectively: BIH as a reductant), and high durability (TON(CO)s of 5232 and 6038, respectively: BIH as a reductant) which are the largest TONs for CO(2) reduction using supramolecular photocatalysts in homogeneous solutions. The absence of negligible accumulation of the mono-reduced form of the photosensitizer indicates fast electron transfer to the catalyst unit(s) through the relatively large bridging ligand and is proposed to contribute to the outstanding photocatalytic properties of the new species, including their durability. The relevant photocatalytic behaviour of the new systems indicates new avenues for the design of extended bridging ligands capable of efficiently and functionally integrating photosensitizers and catalysts towards the preparation of new, larger supramolecular photocatalysts for selective CO(2) reduction. Royal Society of Chemistry 2019-12-14 /pmc/articles/PMC7069366/ /pubmed/32206277 http://dx.doi.org/10.1039/c9sc04532e Text en This journal is © The Royal Society of Chemistry 2020 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Cancelliere, Ambra M.
Puntoriero, Fausto
Serroni, Scolastica
Campagna, Sebastiano
Tamaki, Yusuke
Saito, Daiki
Ishitani, Osamu
Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
title Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
title_full Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
title_fullStr Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
title_full_unstemmed Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
title_short Efficient trinuclear Ru(ii)–Re(i) supramolecular photocatalysts for CO(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
title_sort efficient trinuclear ru(ii)–re(i) supramolecular photocatalysts for co(2) reduction based on a new tris-chelating bridging ligand built around a central aromatic ring
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7069366/
https://www.ncbi.nlm.nih.gov/pubmed/32206277
http://dx.doi.org/10.1039/c9sc04532e
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